WO2008151719A2 - 3-cyclopropyl-4-(3-thiobenzoyl)pyrazoles and their use as herbicides - Google Patents

Abstract

The invention relates to 3-cyclopropyl-4-(3-thiobenzoyl)pyrazoles of general formula (I) and to their use as herbicides. In formula (I), R1, R2, R3, X and Y represent groups such as hydrogen and organic groups such as alkyl. R4 represents hydrogen or a protecting group such as tosyl.

Description

 description

3-Cyclopropyl-4- (3-thiobenzoyl) pyrazoles and their use as herbicides

The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and grass weeds in crops.

It is already known from various publications that certain 4-benzoylpyrazoles have herbicidal properties. Thus, EP 0 352 543 A1 mentions 4-benzoylpyrazoles which may be substituted in the phenyl ring inter alia by a thioro radical. WO 97/41106 and WO 00/03993 refer to 3-cyclopropyl-4-benzoylpyrazoles which may be substituted in the phenyl ring inter alia by a thioro radical. The abovementioned documents do not disclose any examples of substitution of the phenyl ring in the meta position by a thiorest.

However, the compounds known from these publications often show inadequate herbicidal activity. The object of the present invention is therefore to provide herbicidally active compounds with improved herbicidal properties compared with the compounds known from the prior art.

It has now been found that certain 4-benzoylpyrazoles, which are substituted in the 3-position by a cyclopropyl group and whose phenyl ring in the 3-position carries a substituted sulfenyl, sulfinyl or sulfonyl group, are particularly suitable as herbicides. An object of the present invention are 3-cyclopropyl-4- (3-thiobenzoyl) pyrazoles of the formula (I) or salts thereof

wherein

R ¹ is (C ¹ -C ₄ ) -alkyl,

R ² is halogen or (C 1 -C ₄ ) -alkyl,

R ³ is (C ₃ -C ₈ ) -cycloalkyl, (C ₃ -C ₈ ) -cycloalkyl- (C ₁ -C ₉ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) - alkynyl, (CrC ₆₎ -haloalkyl, (C ₃ -C ₈₎ -Halogencycloalkyl- _(Ci-C9) alkyl, (C ₂ - C ₆₎ haloalkenyl, (C ₂ -C ₆₎ -haloalkynyl, (C ₂ -C ₆ ) -nitroalkyl, phenyl, (C ₃ -C ₈ ) -cycloalkoxy- (C ₁ -C ₉ ) -alkyl _I (C ₃ -C ₈ ) -cycloalkyl- (C ₁ -C ₉ ) -alkoxy- (C ₁ -C ₉₎ alkyl, (C _{r C6)} - alkoxy (C _r C ₉₎ alkyl, (C ₂ -C ₆₎ alkenyloxy (-C ₉₎ alkyl, _(C2 -Ce ) -AIkJn ^ oxy- (C ₁ -C ₉₎ - alkyl, (CrC ₆₎ haloalkoxy _(Ci-C9) alkyl, (C ₃ -C ₈₎ halocycloalkyl (C _r -C ₉₎ alkoxy ₍₉ CrC) alkyl, (C ₂ -C ₆₎ -Halogenalkenyloxy- _(Ci-C9) alkyl, (C ₂ -C ₆₎ -Halogenalkinyloxy- ₍₉ CrC) alkyl, (C ₂ -C ₆₎ Nitroalkoxy- (C 1 -C ₉ ) -alkyl, phenyloxy- (C 1 -C ₉ ) -alkyl, where the phenyl group is in each case represented by m identical or different radicals selected from the group consisting of (C 1 -C ₃ ) -alkyl, halogen, nitro, ( CrC ₃ ) -alkoxy may be substituted,

R ⁴ is hydrogen, (C ₁ -C ₆ ) -alkylsulfonyl, (C ₁ -CO-AIkOXy- (C ₁ -C ₆ ) -alkylsulfonyl, or in each case by m identical or different radicals from the group consisting of halogen, (C ₁ -C ₄₎ -alkyl and (CrC ₄₎ -alkoxy substituted phenylsulfonyl, thien-2-ylsulfonyl, benzoyl, (ethylthio) carbonyl, benzoyl, (CrC ₆₎ alkyl or benzyl,

X and Y are independently hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, (C _{r C6)} alkyl, (C _r C ₆₎ -haloalkyl, (C ₂ -C ₆₎ alkenyl, (C ₂ - C ₆ ) -haloalkenyl, (C ₂ -C ₆ ) -alkynyl, (C ₃ -C ₆ ) -haloalkynyl, (C ₃ -C ₆ ) -cycloalkyl, OR ⁵ , Methylsulfonylethoxymethyl, methylsulfonylethylsulfonylmethyl, methoxyethylsulfonylmethyl, OCOR ⁵ , OSO ₂ R ⁵ , S (O) _n R ⁵ , SO ₂ OR ⁵ , SO ₂ N (R ⁵ ) ₂ , (C ₁ -C ₃ ) -alkoxy- (CrC ₃ ) - alkoxyMCrC ₃ ) -alkyl, NR ⁵ SO ₂ R ⁵ , NR ⁵ COR ⁵ , (C _r C ₆ ) -alkyl-S (O) _n R ⁵ , (dC ₆ ) -alkyl-OR ⁵ , (C _r C ₆ ) alkyl-OCOR ^5, (Ci-C ₆₎ alkyl-OSO2R ^5, (C ₁ -C ₆₎ - alkyl-SO ₂ OR ^5, (C _r C ₆₎ alkyl-SO ₂ N (R ⁵⁾ ₂ or (C _r C ₆ ) alkyl-NR ⁵ COR ⁵ ;

R ⁵ is hydrogen, (C ₁ -Ce) -alkyl ₁ (C ₂ -C ₆₎ alkenyl, (C ₂ -C ₆₎ -alkynyl, (C ₃ -C ₆₎ - cycloalkyl, phenyl or phenyl (C -ι-C ₆ ) -alkyl, where the six last mentioned radicals are represented by s radicals of the group hydroxy, mercapto, amino, cyano, nitro, rhodano, OR ⁶ , SR ⁶ , N (R ⁶ ) ₂ , NOR ⁶ , OCOR ⁶ , SCOR ^6, NR ⁶ COR ^6, CO ₂ R ^6, COSR ^6, CON (R ⁶⁾ _2, (C) -C ₄ - Alkyliminooxy, (CRC4) -Alkoxyamino, (CrC ₄₎ alkylcarbonyl, (CrC ₄₎ - Alkoxy- (C ₂ -C ₆ ) alkoxycarbonyl and (C ₁ -C ₄ ) -alkylsulfonyl;

R ⁶ is hydrogen, (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl or (C ₂ -C ₆ ) -alkynyl,

m is 0, 1, 2, 3, 4 or 5,

n is O, 1 or 2,

q is O, 1, 2, 3, 4 or 5,

s is 0, 1, 2 or 3,

with the proviso that R ^{3 is} not (C ₁ -C ₆ ) -haloalkyl when n is O.

In the case where R ^{4 is} hydrogen, the compounds of the formula (I) according to the invention can occur in different tautomeric structures, depending on external conditions, such as solvent and pH:

Depending on the nature of the substituents, the compounds of the general formula (I) contain an acidic proton which can be removed by reaction with a base. Suitable bases are, for example, hydrides, hydroxides and carbonates of lithium, sodium, potassium, magnesium and calcium and ammonia and organic amines such as triethylamine and pyridine. Likewise, salts can be formed by addition of organic acids, such as formic or acetic acid, and inorganic acids, such as phosphoric, hydrochloric or sulfuric acid. Such salts are also the subject of the invention.

In formula (I) and all subsequent formulas, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl. Halogen is fluorine, chlorine, bromine or iodine. Tosyl means 4-methylphenylsulfonyl. If a group is repeatedly substituted by radicals, it is to be understood that this group is substituted by one or more identical or different radicals.

Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur. Likewise, stereoisomers occur when n is 1. Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention also relates to all stereoisomers and mixtures thereof which include but are not specifically defined by the general formula (I).

Preference is given to compounds of the general formula (I) in which

R ¹ is (C ¹ -C ₄ ) -alkyl,

R ² is halogen, methyl or ethyl,

R ³ is cyclopropyl, cyclopropylmethyl, cyclopropylmethoxyethyl, methoxyethyl, methoxypropyl, ethoxyethyl,

R ⁴ is hydrogen, n-propylsulfonyl, phenylsulfonyl, methoxyethylsulfonyl, benzoylmethyl, benzoyl, 4-methylbenzoylmethyl, (ethylthio) carbonyl, 4-methylphenylsulfonyl, thien-2-ylsulfonyl,

X is nitro, halogen, (C 1 -C ₄ ) -alkyl, trifluoromethyl, (C 1 -C ₄ ) -alkoxy, methylsulfonyl, methoxymethyl, methoxymethoxymethyl, ethoxyethoxymethyl, ethoxymethoxymethyl, methoxyethoxymethyl, methoxypropoxymethyl, Methylsulfonylmethyl, methylsulfonylethoxymethyl, methoxyethylsulfonylmethyl, methylsulfonylethylsulfonylmethyl,

Y is halogen, trifluoromethyl, (C 1 -C ₄ ) -alkoxy, methylsulfonyl or ethylsulfonyl,

n is 0, 1 or 2,

q means 0, 1 or 2.

Particular preference is given to compounds of the general formula (I) in which

R ¹ is methyl or ethyl,

R ³ is cyclopropyl, cyclopropylmethyl, cyclopropylmethoxyethyl, methoxyethyl, methoxypropyl, ethoxyethyl,

R ⁴ is hydrogen, n-propylsulfonyl, phenylsulfonyl, methoxyethylsulfonyl, benzoylmethyl, benzoyl, 4-methylbenzoylmethyl, (ethylthio) carbonyl, 4-methylphenylsulfonyl, thien-2-ylsulfonyl,

X is nitro, bromine, chlorine, fluorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, methoxymethyl, methoxymethoxymethyl, ethoxyethoxymethyl, ethoxymethoxymethyl, methoxyethoxymethyl,

Methoxypropoxymethyl, methylsulfonylmethyl, methylsulfonylethoxymethyl, methoxyethylsulfonylmethyl, methylsulfonylethylsulfonylmethyl,

Y is bromine, chlorine, fluorine, trifluoromethyl, methoxy, methylsulfonyl or ethylsulfonyl,

n is 0, 1 or 2, means 0.

In all of the formulas below, the substituents and symbols, unless otherwise defined, have the same meaning as described for formula (I).

Compounds according to the invention in which R ^{4 is} hydrogen can be synthesized, for example, by the method disclosed in Scheme 1 and known from BS Jensen (Acta Chemica Scandinavica 13 (1959), 1668-1670) by base-catalyzed reaction of a benzoic acid halide (IM) with a pyrazolone ( II) or in accordance with the method given in Scheme 2 and known for example from EP-A 0 186 117 by base-catalyzed reaction of a benzoic acid halide (III) with a pyrazolone (II) and subsequent rearrangement.

Scheme 1

(II) (III)

Scheme 2

According to Scheme 3, compounds according to the invention in which R ^{4 has} a meaning other than hydrogen are expediently obtained from the compounds obtainable according to Scheme 1 or 2 by base-catalyzed reaction with a suitable acylating agent R ⁴ -Z of the formula (V) in which Z is a leaving group how halogen is produced. Such methods are known to those skilled in principle and described for example in DOS 25 13 750.

Scheme 3

Compounds of the invention can also be prepared according to the method disclosed in Scheme 4 and known from WO 98/42678 by reacting a pyrazolone (M) and a halo-benzoic acid chloride (IJIa) ₁ subsequent nucleophilic aromatic substitution by a thio compound HS-R ³ and optionally oxidation of the thio group getting produced. In this L means, for example, chlorine, bromine, iodine or trifluoromethylsulfonyl. Such substitution reactions are known in the art and described, for example, in Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E 11, Extension and follow-up volumes to the fourth edition 1985, p 174 et seq.

Scheme 4

The abovementioned compounds of the formula (III) can be prepared, for example, by reaction with acid chlorides, such as thionyl chloride, from the corresponding benzoic acids of the formula (IIIb) according to methods known to the person skilled in the art.

Compounds of the formula (IIIb) can be prepared, for example, according to Scheme 6: For this purpose, a 3-amino derivative of the formula (IIIc) is diazotized in a first step and then reacted with potassium ethylxanthogenate and subsequent saponification to give a 3-thio derivative of the formula (IIId). Such reactions are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E 9, fourth edition 1955, p 12 ff. In a second step, the 3-thio derivatives of the Forme \ (IUd) with Alkylating reagents are alkylated by nucleophilic substitution on a saturated carbon atom or by a conjugate addition to an acceptor-substituted olefin to a derivative of formula (MIe). Such reactions are described for example in Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E 11, Extension and follow-up volumes to the fourth edition 1985, p 165 ff. A subsequent oxidation of the compounds of formula (MIe) leads to those of formula (MIb) wherein n is 1 or 2.

Scheme 6

Compounds of formula (III) and (IIIb) ₁ wherein X, Y and n are as defined for formula (I) are novel and also subject matter of the present application.

The starting compounds used in the above schemes are either commercially available or can be prepared by methods known per se. For example, the pyrazolones of the formula (II) can be prepared according to the methods described in EP-A 0 240 001 and J. Prakt. Chem. 315. 382, (1973) and the benzoic acids of the formula (III) and the benzoyl chlorides of the formula (IIIa) are prepared by the processes described in EP-A 0 527 036 and WO 03/014071.

The compounds of the formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It is usually irrelevant whether the substances are applied in the pre-sowing, pre-emergence or postemergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species. On the side of the monocotyledonous weed species, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annuelle group and on the side of perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten are well detected. In dicotyledonous weed species, the spectrum of activity extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon on the annall side and Convolvulus, Cirsium, Rumex and Artemisia to perennial weeds. Harmful plants occurring under the specific culture conditions in rice such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the active compounds according to the invention. If the compounds according to the invention are applied to the surface of the earth before germination, then either weeding out the weed seedlings completely or the weeds grow up to the cotyledon stage, but then stop their growth and eventually die off after three to four weeks. Upon application of the active ingredients to the green parts of the plants postemergence also occurs very quickly after treatment, a drastic halt in growth and the weed plants remain in the existing stage of application growth stage or die after a certain time completely off, so that in this way one for the crops harmful weed competition is eliminated very early and sustainably. In particular, the compounds according to the invention show an outstanding activity against Apera spica venti, Chenopodium albuni, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica and Viola tricolor.

Although the compounds of the invention have excellent herbicidal activity against mono- and dicotyledonous weeds

Crops of economically important crops such as e.g. Wheat, barley, rye, rice, maize, sugar beet, cotton and soya only marginally or not at all damaged. In particular, they have excellent compatibility in cereals, such as wheat, barley and maize, especially wheat. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in agricultural crops or in ornamental plantings.

Due to their herbicidal properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example, by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens such as certain plant diseases

Insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern, for example, the crop in terms of quantity, quality, Shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.

Preference is given to the use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, e.g. of cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables. Preferably, the compounds of the formula (I) can be used as herbicides in crop plants which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by genetic engineering methods (see eg EP-A-0221044, EP-A-0131624). In several cases, for example, genetic engineering of crops for modification of the starch synthesized in the plants (eg WO 92/11376, WO 92/14827, WO 91/19806), transgenic crop plants which have been found to be active against certain glufosinate-type herbicides (cf. eg EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659), transgenic crop plants, for example cotton, having the ability Bacillus to produce thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP-A-0142924, EP-A-0193259). Transgenic crop plants with modified fatty acid composition (WO 91/13972). Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; See, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. By means of the above-mentioned standard methods, e.g. Base exchanges are made, partial sequences removed or natural or synthetic sequences added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments.

The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.

For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical. In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. However, to achieve localization in a particular compartment, for example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may in principle be plants of any plant species, i. both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

In the application of the active compounds according to the invention in transgenic crops, in addition to the effects observed in other crops against harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled , Altered application rates that can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, as well as influence of growth and yield of transgenic crops. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

In addition, the substances according to the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's own metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, such as through Triggering of desiccation and stunting are used. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. Another object of the invention therefore also herbicidal agents containing compounds of formula (I). The compounds of the formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of microspray, spray , Elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvent Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopaedia of Surface Active Agents", Chem. Pub !. Co. Inc., NY 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Publishing company, Stuttgart 1976; Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance. polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, 2,2'-dinaphthylmethane-6,6'-disulphonic acid sodium (sodium sulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurine) the wettable powders, the herbicidal active ingredients are finely ground, for example in conventional equipment such as hammer mills, blower mills and air jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid ester.

Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding by means of commercially available bead mills and, if appropriate, addition of surfactants, as already listed above, for example, in the other formulation types.

Emulsions, for example oil-in-water emulsions (EW) _1, can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as already listed above for the other formulation types.

Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.

Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the preparation of plate, fluid bed, extruder and spray granules, see e.g. Process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further details on the formulation of crop protection agents see, e.g. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York,

1961, pages 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103. The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I). In wettable powders, the active ingredient concentration is for example about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.

On the basis of these formulations, combinations with other pesticidally active substances, such as e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.

For example, known active compounds can be used as combination partners for the active compounds according to the invention in mixture formulations or in a tank mix, as described, for example, in Weed Research 26, 441-445 (1986) or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and cited therein. As known herbicides which can be combined with the compounds of the formula (I), for example, the following active ingredients are mentioned (Note: The compounds are either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a common code number): acetochlor; acifluorfen; aclonifen; AKH 7088, ie methyl [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and acetic acid; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS ₁ ie ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurones (DPX-A8947); aziprotryn; barban; BAS 516H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butraline; butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chloφropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its

Ester derivatives (e.g., clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; Cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (e.g., butyl ester, DEH

112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, i.

5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; Ethidimuron; ethiozin; ethofumesate; F5231, i. N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide; ethoxyfen and its esters (e.g.

Ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and its esters, eg fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, eg fluazifop-butyl and fluazifop-P-butyl \; ϋuchloraϊin; flucarbazone; flufenacet; flumetsulam; flumeturon; flumiclorac and its esters (eg, pentyl ester, S-23031); flumioxazine (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; foramsulfuron; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; halosulfuron and its esters (eg, methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazapyr; imazamethabenz-methyl; imazaquin and salts like that

Ammonium salt; ioxynil; imazethamethapyr; imazethapyr; imazosulfuron; iodosulfuron-methyl-sodium; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; mesosulfuron; mesotrione; metamitron; metazachlor; metham; methabenzthiazuron; methazole; methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monolinuron; monuron; monocarbamide dihydrogen sulfates; MT 128, i.

6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenisopham; phenmedipham; picloram; pinoxaden; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propoxycarbazone; Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinate; pyrazon; pyrasulfotole; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac (KIH-

2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and theirs Ester derivatives, eg quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -

4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn;

SN 106279, i. 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulcotrione; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; tembotrione; terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, i. N, N -diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiencarbazone; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiobencarb; thifensulfuron-methyl; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trfetazine; trifluralin; triflusulfuron and esters (e.g., methyl esters, DPX

66037); trimeturon; tsitodef; vernolate; WL 110547, i. 5-phenoxy-1- [3-

(trifluoromethyl) -phenyl] -1H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; Dowco-535; DK-8910; V-53482; PP-600;

MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.

For use, the formulations present in commercial form are optionally diluted in the usual manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.

The following examples illustrate the invention. A. Chemical examples

Preparation of 3-Cyclopropyl-4- (3-cyclopropylmethylthio-2-methyl-4-methylsulfonylbenzoyl) -5-hydroxy-1-methylpyrazole (Example Nos. 1 to 38) Step 1: 3-Mercapto-2-methyl-4 -methylsulfonylbenzoesäure

Room temperature (RT) increase. For work-up, 150 ml of 1 M HCl were carefully added. A solution of 2.03 g (50.9 mmol) of NaOH in 60 ml of water was treated with 11.0 g (48.0 mmol) of 3-amino-2-methyl-4-methylsulfonylbenzoic acid (synthesis described by TL Siddall et al in Pest Management Science (2002), 58 (12), 1175-1186). Then, 3.31 g (48.0 mmol) of sodium nitrite was added. The solution was stirred at 5 - 8 ⁰ C added to a mixture of concentrated HCl and ice was added dropwise. The mixture was stirred for 15 minutes at this temperature and then neutralized with sodium acetate. The contents were then added dropwise to a 70 - located 80 ⁰ C solution of 21:54 g (134.3 mmol) potassium ethyl xanthogenate in 80 ml of water. The mixture was stirred for 15 minutes at 80 ⁰ C and then acidified at RT for workup with 1 M HCl. After five minutes, it was decanted off and to the residue was added 85 ml of 10% sodium hydroxide solution. The mixture was heated, whereby distillate formed with the aid of a distillation head was removed so that an internal temperature of 100 ^° C. could be reached. After the mixture was heated at this temperature for 1.25 hours, HPLC analysis indicated that the reaction had gone to completion. Then, 21 ml of a saturated sodium hydrogen sulfite aqueous solution was added, and the mixture was heated at 100 ^° C. for 10 minutes. For workup, the cooled reaction mixture was acidified with 1 M HCl, cooled to 0 - 5 ⁰ C and filtered under nitrogen atmosphere. 10 g of a solid were isolated; a 1 H NMR spectrum indicated the identity of the product.

Step 2: 3-Cyclopropylmethylthio-2-methyl-4-methylsulfonylbenzoic acid 9.0 g (36.5 mmol) of 3-mercapto-2,4-dimethylsulfonylbenzoic acid were dissolved in 70 ml of N, N-dimethylformamide (DMF) under a nitrogen atmosphere and then added in portions with 3.07 g (76.7 mmol, 60 wt .-% purity) NaH. The Mixture was stirred for 15 minutes at RT, then 5.43 g (40.2 mmol) of cyclopropylmethyl bromide were slowly added dropwise. The mixture was stirred at RT for 16 h. For workup, the solvent was removed in vacuo and the residue was taken up in a mixture of water and methanol. 8 g (200 mmol) of NaOH were added and the reaction mixture was stirred at RT until HPLC analysis indicated no more cyclopropylmethyl ester. The mixture was freed from the solvents, water was added to the residue, the aqueous phase was acidified with 1 M HCl and then extracted twice with ethyl acetate (EA). The combined organic phases were dried, filtered and freed from the solvent. The residue was washed with n-heptane. The heptane was decanted off and the residue was dried under vacuum. 11.1 g of the pure product were isolated.

Step 3: 3-Cyclopropyl-4- (3-cyclopropylmethylthio-2-methyl-4-methylsulfonylbenzoyl) -5-hydroxy-1-methylpyrazole

190 mg (0.63 mmol) of 3-cyclopropylmethylthio-2-methyl-4-methylsulfonylbenzoic acid were initially charged in 15 ml of dry dichloromethane and admixed with 121 mg (0.95 mmol) of oxalyl chloride and a few drops of DMF. The mixture was stirred for 15 min. heated to reflux, then no gas separation was observed. The contents were cooled to RT and concentrated. The resulting acid chloride was dissolved in 15 ml of acetonitrile and treated with 96 mg (0.70 mmol) of 3-cyclopropyl-5-hydroxy-1-methylpyrazole. Thereafter, 128 mg (1.27 mmol) of triethylamine were slowly added dropwise, and the reaction mixture was stirred at RT for 16 h. 10 drops of acetone cyanohydrin and a spatula tip KCN were added to the enol ester thus obtained. The mixture was stirred at RT for 16 h and was then concentrated. The residue was mixed with 15 ml of dichloromethane and then with 2 ml of 1 M HCl. After phase separation, the organic phase was freed from the solvent. The residue was purified by chromatography to isolate 65.7 mg of clean product.

Preparation of 3-cyclopropyl-4- (3-cyclopropylmethylsulfonyl-2-methyl-4-methylsulfonylbenzoyl) -5-hydroxy-1-methylpyrazole (Example Nos. 1-50) Step 1: S-Cyclopropylmethylsulfonyl-methyl-W-methylsulfonylbenzoic acid 952 mg (3.17 mmol) of S-cyclopropylmethylthio-methylmethylsulfonylbenzoic acid were dissolved in 15 ml of glacial acetic acid. 31 mg (0.095 mmol) Natriumwo \ Framat (V}) were dihydrate was added, then the mixture was heated to 60 ⁰ C. At this temperature, 1.44 g (30%, 12.7 mmol) of an aqueous

Hydrogen peroxide solution added dropwise. The mixture was stirred at this temperature for two days. It was then cooled and poured onto water for work-up. The mixture was extracted twice with EA, the combined organic phases were washed with an aqueous saturated sodium bisulfite solution, and after analytically detecting the absence of peroxides, the mixture was dried, filtered and freed of the solvents under vacuum. 744 mg of the product was isolated.

Step 2: Synthesis of 3-cyclopropyl-4- (3-cyclopropylmethylsulfonyl-2-methyl-4-methylsulfonylbenzoyl) -5-hydroxy-1-methylpyrazole

149 mg (0.45 mmol) of 3-cyclopropylmethylsulfonyl-2-methyl-4-methylsulfonylbenzoic acid were initially charged in 15 ml of dry CH ₂ Cb and mixed with 114 mg (0.90 mmol) of oxalic acid dichloride and a few drops of DMF. The mixture was stirred for 15 min. heated to reflux, then no gas separation was observed. The contents were cooled to RT and concentrated. The resulting acid chloride was dissolved in 15 ml of dry dichloromethane and admixed with 68 mg (0.49 mmol) of 3-cyclopropyl-5-hydroxy-1-methylpyrazole. Thereafter, 91 mg (0.90 mmol) of triethylamine were slowly added dropwise, and the reaction mixture was stirred at RT for 16 h. For work-up, 2 ml of 1 M HCl were added, and after the phase separation, the organic phase was freed from the solvent. The enol ester thus obtained was taken up in 15 ml of acetonitrile and mixed with 10 drops of acetone cyanohydrin and a spatula tip KCN. The mixture was stirred at RT for 16 h and was then concentrated. The residue was mixed with 15 ml of CH ₂ Cl ₂ and then with 2 ml of 1 M HCl. After phase separation, the organic phase was freed from the solvent. The residue was purified by chromatography, whereby 103 mg of clean product were isolated. Preparation of 4- (2-chloro-3- (2-methoxyethyl) thio-4-methylsulfonylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole (Example Nos. 1-3) Step 1: Synthesis of 2- ChJor-3- (2 ^{'-methoxyethy))} thio-4-methylsulfonylbenzoic acid 5.0 g (19.8 mmol) of 2-chloro-3-fluoro-4-methylsulfonylbenzoic acid (synthesis described in WO 98/42648) was taken up in 40 ml DMF. 871 mg (21.8 mmol, 60% by weight purity) of NaH were added. The mixture was stirred at RT for 30 minutes. Thereafter, a reaction mixture containing the sodium salt of 2-methoxyethanethiol (prepared from a solution of 2.19 g (23.7 mmol) of 2-methoxyethanethiol in 10 ml of DMF was added dropwise to a suspension of 950 mg (23.7 mmol, 60% by weight). Purity) was added NaH in 30 ml of DMF, then stirred for 30 minutes at RT), added in portions. The temperature was kept below 30 ⁰ C. The reaction mixture was stirred at RT for 16 h, diluted with water for work-up and washed with diethyl ether. The aqueous phase was acidified with 1 M HCl and extracted with tert-butyl methyl ether. The organic phase was dried and filtered. In addition, the aqueous phase was extracted with EA and the organic phase was also dried and filtered. The filtrates of the organic phases were combined and freed from the solvent. The residue was dried under vacuum and purified by chromatography. 4.8 g of the clean product were obtained.

Step 2: Synthesis of 4- (2-chloro-3- (2-methoxyethyl) thio-4-methylsulfonylbenzoyl) -

3-cyclopropyl-5-hydroxy-1-methylpyrazole

550 mg (1.69 mmol) of 2-chloro-3- (2-methoxyethyl) thio-4-methylsulfonylbenzoic acid were initially charged in 20 ml of dry CH ₂ Cl ₂ and admixed with 430 mg (3.39 mmol).

Oxalic acid dichloride and two drops of DMF added. The mixture was stirred for 15 min. heated to reflux. The contents were cooled to RT and concentrated. The resulting acid chloride was dissolved in 20 ml of dry CH ₂ Cl _{2 and} treated with 257 mg (1.86 mmol) of 3-cyclopropyl-5-hydroxy-1-methylpyrazole. Thereafter, 343 mg (3.39 mmol) of triethylamine were slowly added dropwise, and the reaction mixture was stirred at RT for 16 h. For work-up, 5 ml of 1 M HCl were added, and after the phase separation, the organic phase was freed from the solvent. Of the The residue was purified by chromatography, and the enol ester thus obtained was taken up in 20 ml of acetonitrile and treated with 343 mg (3.39 mmol) of triethylamine, eight drops of acetone cyanohydrin and a spatula tip KCN. The mixture was stirred at RT for 16 h and was then concentrated. The residue was added with 20 ml of CH ₂ Cb and then with 5 ml of 1 M HCl. After

Phase separation, the organic phase was freed from the solvent. The residue was purified by chromatography to isolate 579 mg of clean product.

Preparation of 4- (2-chloro-3- (2-methoxyethyl) sulfinyl-4-methylsulfonylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole (Example Nos. 1-9) and 4- (2-chloro -3- (2-methoxyethylsulfonyM-methylsulfonylbenzoyl-S-cyclopropyl-δ-hydroxy-i-methylpyrazole (Example Nos. 1-15) 193 mg (0.43 mmol) of 4- (2-chloro-3- (2-methoxyethyl ) Thio-4-methylsulfonylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole were dissolved in 20 ml of CH ₂ Cl ₂ and then treated with 321 mg (70 wt .-% purity, 1.30 mmol) Metachlorperbenzoesäure The mixture was stirred at RT for 16 h and worked up by dilution with CH ₂ Cl ₂ and washing with 10% aqueous sodium hydrogen sulfite solution, keeping the pH of the aqueous phase in the acidic range with 1 M HCl Phase separation and, after the analytical proof of the absence of peroxides, the organic phase is dried, filtered and freed from solvent The residue was separated by chromatography, wherein 9.6 mg of pure 4- (2-chloro-3- (2-methoxyethyl) sulfinyl-4-methylsulphonylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole and 71.6 mg of clean 4- (2-chloro-3- ( 2-methoxyethyl) sulfonyl-4-methylsulfonylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole.

Preparation of 3-Cyclopropyl-5-hydroxy-4- (3- (2-methoxyethyl) thio-2-methyl-4-trifluoromethylbenzoyl) -1-methylpyrazole (Example No. 1-2091) Step 1: Synthesis of 3- fluoro-2-methyl-4-trifluoromethyl-benzoic acid

25.0 g (120.1 mmol) of 3-fluoro-4-trifluoromethylbenzoic acid were dissolved in 250 ml of dry THF and 100.9 ml (2.5M in hexane, 252.3 mmol) of n-butyllithium were added at a temperature of -40 ⁰ C dropwise. The mixture was stirred for 3.5 h, then a solution of 51.2 g (360.4 mmol) iodomethane in 50 ml dry THF was added. The mixture was stirred for 16 h, after which the temperature rose slowly to RT after half an hour. For workup, 150 ml of 1 M HCl were added carefully. The mixture was extracted with diethyl ether, then the organic phase was extracted with 1 M NaOH. The aqueous phase was acidified and then extracted with diethyl ether. The organic phase was washed with water, dried and concentrated. The residue was stirred with n-heptane and the solid was separated via filtration. 13.5 g of the clean product were isolated.

Step 2: Synthesis of 3- (2-methoxyethyl) thio-2-methyl-4-trifluoromethylbenzoic acid

1.45 g (6.53 mmol) of 3-fluoro-2-methyl-4-trifluoromethylbenzoic acid were initially charged in 40 ml of DMF. 809 mg (20.2 mmol) of NaH were added portionwise. To complete the gas separation, 1.20 g (13.1 mmol) of 2-methoxyethanethiol were added dropwise. The mixture was stirred at RT for 10 minutes and then heated to 80 ^° C. for 15 hours. The reaction mixture was cooled, concentrated in vacuo, water was added to workup and acidified with 1 M HCl. The product precipitated and was separated via filtration. The product was then washed with water and n-heptane. 1.7 g of the clean product was isolated.

Step 3: Synthesis of 3-cyclopropyl-5-hydroxy-4- (3- (2-methoxyethyl) thio-2-methyl-4-trifluoromethylbenzoyl) -1-methylpyrazole

520 mg (1.77 mmol) of 3- (2-methoxyethyl) thio-2-methyl-4-trifluoromethylbenzoic acid were initially charged in 20 ml of dry CH ₂ Cb and admixed with 449 mg (3.53 mmol) of oxalyl chloride and two drops of DMF. The mixture was stirred for 15 min. heated to reflux, then no gas separation was observed. The contents were cooled to RT and concentrated. The acid chloride thus obtained was dissolved in 20 ml of dry CH ₂ Cb and admixed with 269 mg (1.94 mmol) of 3-cyclopropyl-5-hydroxy-1-methylpyrazole. Thereafter, 358 mg (3.53 mmol) Triethylamine slowly added dropwise, and the reaction mixture was stirred for 16 h at RT. For workup, 5 ml of 1 M HCl were added and after the phase separation was freed from the solvent. The enol ester thus obtained was taken up in 20 ml of acetonitrile after chromatographic purification, and 358 mg (3.53 mmol) of triethylamine were added. Subsequently, eight drops of acetone cyanohydrin and a spatula tip KCN were added. The mixture was stirred at RT for 16 h and was then concentrated. The residue was treated with 20 ml of CH ₂ Cb and then with 5 ml of 1 M HCl. After phase separation was freed from the solvent. The residue was purified by chromatography to isolate 354 mg of clean product.

Preparation of 4- (4-chloro-3'-cyclopropylmethylthio-2-methylbenzoyl) -3-cyclopropyl

5-hydroxy-1-methylpyrazole (Example No. 1-1406)

Step 1: Synthesis of 4-chloro-3- (dimethylaminothiocarbonyloxy) -2-methylbenzoic acid methyl ester

11.0 g (54.8 mmol) of 4-chloro-3-hydroxy-2-methylbenzoic acid methyl ester (synthesis described in DE 10039723) were dissolved under nitrogen in 200 ml of DMF with 12.3 g (109.7 mmol) of 1,4-diazabicyclo [2.2.2] octane and then with 13.6 g (109.7 mmol) of dimethylaminothiocarbonyl chloride. The mixture was stirred at RT for 16 h, for work-up, it was poured onto ice-water. The product precipitated and was separated via filtration. The residue was washed with 1 M HCl. There were 14.7 g of clean product.

Step 2: Synthesis of 4-chloro-3- (dimethylaminocarbonylthio) -2-methylbenzoic acid methyl ester

12.1 g (42.0 mmol) of methyl 4-chloro-3- (dimethylaminothiocarbonyloxy) -2-methylbenzoate were heated to 22O ⁰ C under nitrogen atmosphere in 30 ml of 1, 3-dimethoxybenzene for 6 hours. For workup, the reaction mixture was cooled and concentrated in vacuo. After chromatographic purification of the residue, 5.2 g of clean product were isolated.

Step 3: Synthesis of 4-chloro-3-mercapto-2-methylbenzoic acid 4.80 g (16.7 mmol) of methyl 4-chloro-3- (dimethylaminocarbonylthio) -2-methylbenzoate were admixed in 150 ml of methanol with 6.61 g (85% by weight purity, 100.1 mmol) of KOH and stirred under reflux for two days. The reaction mixture was freed of solvent, and the residue was added with water, then acidified with 1 M HCl, and the solid was separated by filtration. There was obtained 3.2 g of clean product.

Step 4: Synthesis of 4-chloro-3-mercapto-2-methylbenzoic acid methyl ester 3.60 g (17.8 mmol) of 4-chloro-3-mercapto-2-methylbenzoic acid were stirred under nitrogen atmosphere in 50 ml of absolute methanol with 1 ml of concentrated sulfuric acid for 17 h heated to reflux for a long time. The mixture was freed of solvent and the residue was taken up in water. After two extractions with ethyl acetate, the combined organic phases were dried, filtered under nitrogen atmosphere and freed from the solvent. 3.2 g of clean product were isolated.

Step 5: Synthesis of 4-chloro-3-cyclopropylmethylthio-2-methylbenzoic acid methyl ester

1.05 g (4.85 mmol) of methyl 4-chloro-3-mercapto-2-methylbenzoate were admixed with 1.66 g (5.09 mmol) of cesium carbonate in 20 ml of acetonitrile. 687 mg (5.09 mmol) of cyclopropylmethylbromide were slowly added dropwise and the reaction mixture was stirred at RT for 16 h. For workup, the solvent was separated, and the residue was added with water. The mixture was extracted three times with ethyl acetate, the combined organic phases were dried, filtered, and the solvent was removed. 1.2 g of clean product were isolated.

Step 6: Synthesis of 4-chloro-3-cyclopropylmethylthio-2-methylbenzoic acid 1.20 g (4.43 mmol) of methyl 4-chloro-3-cyclopropylmethylthio-2-methylbenzoate were dissolved in 30 ml of methanol with 3 ml of 20 percent strength by wt. Sodium hydroxide solution and stirred for 16 h at RT. For workup, the mixture was concentrated on a rotary evaporator and the residue was taken up in water. It was with 1M HCl, and the product was subsequently filtered off as a solid. 1.1 g of clean product was obtained.

Step 7: Synthesis of 4- (4 ^'-chloro-3' -cyclopropylmethylthio -2 ^{'-methylbenzoyl)} -3-cyclopropyl-δ-hydroxy-1 -methylpyrazol

272 mg (1.06 mmol) of 4-chloro-3-cyclopropylmethylthio-2-methylbenzoic acid were dissolved in 20 ml of dichloromethane with 161 mg (1.17 mmol) of 3-cyclopropyl-5-hydroxy-1-methylpyrazole and a few drops of N, N-4-dimethylaminopyridine added. 244 mg (1.27 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added and the mixture was stirred at RT for 16 h. For work-up, 3 ml of 1M HCl were added and the organic phase was freed from the solvent. The residue was combined in 15 ml of acetonitrile with 214 mg (2.12 mmol) of triethylamine, 10 drops of acetone cyanohydrin and a spatula tip KCN. The reaction mixture was at RT for 16 h and then freed from the solvent. The residue was added to 15 ml of CH 2 Cl 2 with 2 ml of 1 M HCl. The organic phase was freed from the solvent and the residue was then purified by chromatography. 154 mg of clean product were obtained.

Preparation of 4- (4-chloro-3-cyclopropylmethylsulfonyl-2-methylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole (Example No. 1-1418)

78 mg (0.21 mmol) of 4- (4-chloro-3-cyclopropylmethylthio-2-methylbenzoyl) -3-cyclopropyl-5-hydroxy-1-methylpyrazole were dissolved in 20 ml of CH ₂ Cl ₂ with 128 mg (70% by weight). Purity, 0.52 mmol) of metachloroperbenzoic acid. Thereafter, the mixture was stirred at RT for 5 h. For workup, the mixture was washed with 10% aqueous sodium hydrogen sulfite solution. The pH of the aqueous phase was kept in the acidic range, otherwise it was acidified with 1M HCl. Subsequently, after the phase separation and after the analytical detection of the absence of peroxides, the organic phase was dried, filtered and freed from the solvent. The residue was purified by chromatography to give 29.1 mg of clean product. The examples listed in the following tables were prepared analogously to the above-mentioned methods or are obtainable analogously to the methods mentioned above. These compounds are most preferred.

The abbreviations used mean:

Bu = butyl Et = ethyl Me = methyl Pr = propyl c = cyclo i = iso Ph = phenyl

Table A: Compounds of the general formula (I) according to the invention, wherein R ^{1 is} methyl, R ^{4 is} hydrogen and q is zero

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} n-propylsulfony! stands.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} phenylsulfonyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} methoxyethylsulfonyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} benzoylmethyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} 4-methylphenylsulfonyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} thien-2-ylsulfonyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} benzoyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} 4-methylbenzoylmethyl.

Likewise, most preferably all of the above compounds of

Nos. 1-1 to 1-2394 in which R ^{4 is} (ethylthio) carbonyl. B. Formulation Examples 1. Dusts

A dust is obtained by mixing 10 parts by weight of a compound of general formula (I) and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.

2. Dispersible powder

A wettable powder easily dispersible in water is obtained by mixing 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of oleoylmethyltaurine sodium as a wetting and dispersing agent, and grinded in a pin mill.

3. Dispersion concentrate

A dispersion concentrate readily dispersible in water is obtained by adding 20 parts by weight of a compound of the general formula (I) ₁ 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight

Isotridecanolpolyglykolether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ⁰ C) mixed and milled in a ball mill to a fineness of less than 5 microns.

4. Emulsifiable concentrate

An emulsifiable concentrate is obtained from 15 parts by weight of a compound of general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

5. Water-dispersible granules

A water-dispersible granule is obtained by reacting 75 parts by weight of a compound of the general formula (I) 10 lignosulfonic acid calcium,

5 sodium lauryl sulfate,

3 polyvinyl alcohol and

7 Kaolin mixed, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit.

A water-dispersible granule is also obtained by

25 parts by weight of a compound of general formula (I), 5 "2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,

2 "oleoylmethyl tauric acid sodium,

1 "polyvinyl alcohol,

17 "calcium carbonate and

50 "of water homogenized on a colloid mill and pre-crushed, then on a

Milled bead mill and the suspension thus obtained in a spray tower by means of a

Single-substance nozzle atomises and dries.

C. Biological examples

1. Herbicidal action against harmful plants in pre-emergence Seeds or rhizome pieces of monocotyledonous and dicotyledonous harmful plants are placed in sandy loam soil in pots of 9 to 13 cm in diameter and covered with soil. The formulated as emulsifiable concentrates or dusts herbicides are in the form of aqueous dispersions or suspensions or

Emulsions with a water application amount of converted 300 to 800l / ha in a dosage of 320 grams per hectare applied to the surface of the cover soil. Subsequently, the pots are kept for optimal cultivation of the plants in the greenhouse under optimal conditions. The visual evaluation of the damage to the harmful plants takes place 3-4 weeks after the treatment. The compounds of Nos. 1-3, 1-15, 1-44 and 1-1407 show an at least 90% action against Echinochloa crus galli. The compounds of Nos. 1-15, 1-45, 1- 1407 and 1-1419 show at least 90% activity against Abutilon theophrasti. The compounds of Nos. 1-3, 1-45, 1-1406 and 1-1418 show at least 90% activity against Amaranthus retroflexus. The compounds of Nos. 1-44, 1-1406, 1-1407 and 1-1419 show at least 90% action against Stellaria media.

2. Herbicidal action against harmful plants in postemergence

Seeds of monocotyledonous and dicotyledonous weeds are placed in sandy loam soil in cardboard pots, covered with soil and grown in the greenhouse under good growth conditions. Two to three weeks after sowing, the test plants are treated in a trefoil study. The compounds of the invention formulated as wettable powders or as emulsion concentrates are sprayed onto the surface of the green parts of the plant at a rate of 600 to 800 l / ha at a dosage of 80 grams per hectare. The visual evaluation of the damage to the harmful plants takes place 3-4 weeks after the treatment. The compounds of Nos. 1-39, 1-40, 1-1382 and 1-2091 show at least 90% activity against Echinochloa crus galli. The compounds of Nos. 1-3, 1-44 and 1-2091 show at least 90% activity against Abutilon theophrasti. The compounds of Nos. 1-39, 1-40 and 1-1382 show at least 90% activity against Veronica persica. The compounds of Nos. 1-3, 1-38, 1-39, 1-1406 and 1-1407 show at least 90% action against Stellaria media.

3. Comparative Experiments In order to demonstrate the superiority of the compounds of the invention over the known from the prior art compounds (WO 97/41106 and WO 00/03993), the herbicidal activity against harmful plants or the damage to crops under the above conditions in the Vor - and compared postemergence in comparative experiments. The following comparative experiments of Tables 1 to 24 show the superiority of the compounds of the invention over the compounds known from the prior art. The abbreviations used therein mean: harmful plants

ABUTH Abutiion theophrasti ALOMY Alopecurus myosuroides

AMARE Amaranthus retroflexus AVEFA Avena fatua

CHEAL Chenopodium album ECHCG Echinochloa crus galli

GALAP Galium aparine LOLMU Lolium multiflorum

MATIN Matricaria inodora PHBPU Pharitis purpureum

POLCO Fallopia convolvulus STEME Stellaria media

VERPE Veronica persica VIOTR viola tricolor XANST Xanthium strumarium

crops

GLXMA Glycine max (soybean) TRZAS Triticum aestivum (wheat)

ZEAMX Zea mays (corn)

Claims

claims:

1. 3-cyclopropyl-4- (3-thiobenzoyl) pyrazoles of the formula (I) or salts thereof

wherein

R ¹ is (C ¹ -C ₄ ) -alkyl,

R ² is halogen or (C 1 -C ₄ ) -alkyl,

R ³ is (C ₃ -C ₈ ) -cycloalkyl, (C ₃ -C ₈ ) -cycloalkyl- (C ₁ -C ₉ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) - alkynyl, (Ci-C ₆₎ -haloalkyl, (C ₃ -C ₈₎ -Halogencycloalkyl- _(Ci-C9) alkyl, (C ₂ - C ₆₎ haloalkenyl, (C ₂ -C ₆₎ haloalkynyl, (C ₂ -C ₆ ) -nitroalkyl, phenyl, (C ₃ -C ₈ ) -cycloalkoxy- (C ₁ -C ₉ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl- (C ₁ -C ₉ ) -alkoxy) _(Ci-C9) alkyl, (C _{r C6)} - alkoxy (C _r C ₉₎ alkyl, (C ₂ -C ₆₎ alkenyloxy (C ₁ -C ₉₎ alkyl, (C ₂ -Ce) -AlkJn ^ OXy- (C ₁ -C ₉ ) -, alkyl, (Ci-C ₆ ) -haloalkoxy- (Ci-C ₉ ) -alkyl, (C ₃ -C ₈ ) -halocycloalkyl (Ci-C ₉ ) alkoxy- (CrCg) -alkyl, (C ₂ -C ₆ ) -haloalkenyloxy- (Ci-C ₉ ) -alkyl, (C ₂ -C ₆ ) -haloalkynyloxy- (Ci-Cg) -alkyl, (C C ₂ -C ₆ ) -nitroalkoxy- (C ₁ -C ₉ ) -alkyl, phenyloxy- (C ₁ -C ₉ ) -alkyl, where the phenyl group is in each case m equals or different radicals from the group consisting of (C 1 -C ₃ ) -alkyl, Halogen, nitro, (C 1 -C ₃ ) -alkoxy may be substituted,

R ⁴ is hydrogen, (C ₁ -C ₆ ) -alkylsulfonyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₆ ) -alkylsulfonyl, or in each case by m identical or different radicals from the group consisting of halogen, (C ₁ -C ₄ ) -Alkyl and (C 1 -C ₄ ) -alkoxy-substituted phenylsulfonyl, thien-2-ylsulfonyl, (ethylthio) carbonyl, Benzoyl, benzoyl (C 1 -C ₆ ) alkyl or benzyl,

X and Y are independently hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, (Ci-C ₆₎ -alkyl, (CrC ₆₎ -haloalkyl, (C ₂ -C ₆₎ alkenyl, (C ₂ - C ₆ ) -Haloalkenyl, (C ₂ -C ₆ ) -alkynyl, (C ₃ -C ₆ ) -haloalkynyl, (C ₃ -C ₆ ) -cycloalkyl, OR ⁵ , methylsulfonylethoxymethyl, methylsulfonylethylsulfonylmethyl, methoxyethylsulfonylmethyl, OCOR ⁵ , OSO ₂ R ⁵ , S (O) _n R ⁵ , SO ₂ OR ⁵ , SO ₂ N (R ⁵ ) ₂ , (C 1 -C 6 -alkoxy) C 1 -C 6 -alkoxy, C 1 -C 6 -alkyl, NR ⁵ SO ₂ R ⁵ , NR ⁵ COR ⁵ , (dC ₆₎ alkyl S (O) _n R ^5, (d-CeJ-alkyl-OR ^5, (CrC ₆₎ alkyl-OCOR ^5, (C ₁ -C ₆₎ alkyl-OSO2R ^5, (C -C ₆ ) - alkyl-SO ₂ OR ⁵ , (C _r C ₆ ) -alkyl-SO ₂ N (R ⁵ ) ₂ or (C _r C ₆ ) -alkyl-NR ⁵ COR ⁵ ;

R ⁵ is hydrogen, (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, (C ₃ -C ₆ ) -cycloalkyl, phenyl or phenyl- (C -ι-C ₆ ) -alkyl, where the six last mentioned radicals are represented by s radicals of the group hydroxy, mercapto, amino, cyano, nitro, rhodano, OR ⁶ , SR ⁶ , N (R ⁶ ) ₂ , NOR ⁶ , OCOR ⁶ , SCOR ⁶ , NR ⁶ COR ⁶ , CO ₂ R ⁶ , COSR ⁶ , CON (R ⁶ ) ₂ , (C 1) -C ₄ -alkyliminooxy, (C 1 -C ₄ ) -alkoxyamino, (C 1 -C ₄ ) -alkylcarbonyl, (CrC _4- J-alkoxy- (C ₂ -C ₆ ) -alkoxycarbonyl and (C ₁ -C ₄ ) -alkylsulfonyl are substituted;

R ⁶ is hydrogen, (C _{r C6)} alkyl, (C ₂ -C ₆₎ alkenyl or (C ₂ -C ₆₎ alkynyl,

m is O, 1, 2, 3, 4 or 5,

n is O, 1 or 2,

q is O, 1, 2, 3, 4 or 5,

s is 0, 1, 2 or 3,

with the proviso that R ³ is not (CrCβJ haloalkyl when n is O.

2. 3-cyclopropyl-4- (3-thiobenzoyl) pyrazoles according to claim 1, wherein R ¹ is (C ₁ -C ₄ ) -alkyl,

R ² is halogen, methyl or ethyl,

R ³ is cyclopropyl, cyclopropylmethyl, cyclopropylmethoxyethyl, methoxyethyl, methoxypropyl, ethoxyethyl,

R ⁴ is hydrogen, n-propylsulfonyl, phenylsulfonyl, methoxyethylsulfonyl, benzoylmethyl, benzoyl, 4-methylbenzoylmethyl, (ethylthio) carbonyl, 4-methylphenylsulfonyl, thien-2-ylsulfonyl,

X is nitro, halo, (C _{r C4)} alkyl, trifluoromethyl, (CrC ₄₎ -alkoxy, methylsulfonyl, methoxymethyl, methoxymethoxymethyl, ethoxyethoxymethyl, ethoxymethoxymethyl, methoxyethoxymethyl, Methoxypropoxymethyl,

Methylsulfonylmethyl, methylsulfonylethoxymethyl, methoxyethylsulfonylmethyl, methylsulfonylethylsulfonylmethyl,

Y is halogen, trifluoromethyl, (C 1 -C ₄ ) -alkoxy, methylsulfonyl or ethylsulfonyl,

n is 0, 1 or 2,

q means 0, 1 or 2.

3. 3-Cyclopropyl-4- (3-thiobenzoyl) pyrazoles according to claim 1, wherein

R ¹ is methyl or ethyl,

R ³ is cyclopropyl, cyclopropylmethyl, cyclopropylmethoxyethyl, methoxyethyl, methoxypropyl, ethoxyethyl, R ⁴ is hydrogen, n-propylsulfonyl, phenylsulfonyl, methoxyethylsulfonyl, benzoylmethyl, benzoyl, 4-methylbenzoylmethyl, (ethylthio) carbonyl, 4-methylphenylsulfonyl, thien-2-ylsulfonyl,

X is nitro, bromine, chlorine, fluorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylsulfonyl, methoxymethyl, methoxymethoxymethyl, ethoxyethoxymethyl, ethoxymethoxymethyl, methoxyethoxymethyl, methoxypropoxymethyl, methylsulfonylmethyl, methylsulfonylethoxymethyl, methoxyethylsulfonylmethyl, methylsulfonylethylsulfonylmethyl,

Y is bromine, chlorine, fluorine, trifluoromethyl, methoxy, methylsulfonyl or ethylsulfonyl,

n is 0, 1 or 2,

q means 0.

4. A herbicidal composition, characterized by a herbicidally active content of at least one compound of the formula (I) according to one of claims 1 to 3.

5. A herbicidal composition according to claim 4 in admixture with formulation auxiliaries.

6. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound of formula (I) according to any one of claims 1 to 3 or a herbicidal composition according to claim 4 or 5 on the plants or on the location of undesired plant growth applied.

7. Use of compounds of the formula (I) according to any one of claims 1 to 3 or of herbicidal compositions according to claim 4 or 5 for controlling unwanted plants.

8. Use according to claim 7, characterized in that the

Compounds of formula (I) for controlling undesirable plants in crops of crops are used.

9. Use according to claim 8, characterized in that the crops are transgenic crops.

10. Compounds of the formula (III)

wherein X, Y and n are as defined in any one of claims 1 to 3.

11. Compounds of the formula (IIIb)

wherein X, Y and n are as defined in any one of claims 1 to 3.